Vat dyestuffs of the anthraquinone series



Patented July 2,1940

" UNITED STATES VAT nYEs'rUFFs PATENTjorrlcs A OF THE ANTHRAQUINONE SERIES Otto Schlichting, Ludwigshafen-on-the-Rhine,

Germany, assignor to General Aniline & Film Corporation, a corporation of Delaware No Drawing. Original application'July 7; 1937,

Serial No. 152,375. Divided and this application December 16, 1938, Serial No. 246,125. v In Germany July 8, 1936 6 Claims. (01. 260307) The present invention relates to vat dyestuffs of the anthraquinone series and has been divided out from my copending application Ser. No. 152,375, filed July '7, 1937, now U. 5. Patent 2,168,174, issued August 1, 1939.

I have found that compounds of the anthraquinone series having the general composition (in which A is the radical of an anthraquinone, X is oxygen, sulphur, selenium, tellurium or an iminogroup, R is a radical of the benzene series, Y is an imino group or oneof the groups CONH or N'HCO and Z is a cyclic radical) are valuable vat-dyestuffs.

The said compounds may be prepared b-y causing compounds of the structure x A/ \CRW1 N Y Y to react with compounds of the structure Z-W2,

W1 and W2 being halogen, a 'hydroxy, amino or cyano group or a carboxylic acid, carboxylic acid amide, carboxylic acid anhydride or carboxylic acid halide group and the initial materials be so selected that the groups W1 and W2 allow the radical 36 to join with the radical Z by means of Y, or

pounds which contain at least one exchangeable 1 hydrogen atom attached to nitrogen (as for example primary or secondary amino derivatives of cyclic compounds), or amides of cyclic carboxylic acids may be caused to react with anthraquinoneazoles of the said kind. The compounds thus obtainable are either imino compounds or carboxylic acid amides.

The carboxylic acid amides are obtained when anthraquinoneazoles having at least one nonhydrogenated ring incapable of vatting attached to the azole ring which contains an amino group 1 with a replaceable hydrogen atom are treated with acylating agents containing a cyclic radical Z. Furthermore anthraquinoneazoles of the said kind which contain an amino group in the ring attached to the azole ring may also be caused to react with amides of-cyclic carboxylic acids in the presence," of acid agents. Cyclic amino compounds having at least one replaceable hydrogen atom may also be caused to react with anthraquinoneazoles containing at least one nonhydrogenated ring incapable of vatting attached to the azole ring and in the ring a carboxyl group in a form which renders it capable of forming acid amides.

Anotherway of; preparing the new ,dyestuff consists in causing cyclic compounds containing, attached .byway-ofan amino or carboxylic amide group, at least onenon-hydrogenated ring incapable of vatting and in this ring a carboxylic, carboxylicacid amide, carboxylic acid halide, aldehyde, die or tri-halogenmethyl group, to react with aminoanthraquinones-whicli' are capable of reacting with the said compounds with the formation of an azole ring. In this connection there may be mentioned for example aminoanthraquinones containing halogen or a hydroxy, mercapto, seleno, telluro or amino group in ortho-position to the amino group. The prep aration of thiazoles may also be carried out by efiecting thereaction with the aminoanthraquinone while simultaneously or subsequently adding sulphur .or sulphurizing agents. A similar procedure holds good for the preparation of the selenazoles. In many cases, other processes usual ,forthe preparation of azoles may be used.

The anthraquinoneazoles described as initial materials at .the commencement of the third paragraph of the vdescription may contain the azole ring at any two adjacent positions of the anthraquinone. In addition to the groups necessary for the reaction contained in the ring situated on the azole ring, the compounds may contain any desired atoms or groups in the said ring or in the anthraquinone part of the molecule; They may be obtained by the processes usual for the preparation of anthraquinone azoles. The compounds the radical Z of which is attached to the carbon atom of the azole ring by the bridge R'Y- may belong to the benzene, naphthalene, anthracene, pyrene, perylene, anthraquinone, anthrapyrimidine, anthanthrone,

pyranthrone, dibenzpyrenequinone, naphthindenone, benzanthrone, benzanthraquinone, azanthraquinone, azabenzanthrone, anthrapyridone, pyrazolanthrone, thiazolanthrone, anthraquinonebenzacridone, anthraquinonethioxanthrone series or also to the azanaphthalene, azanthracene, azaphenanthrene, azapyrene, azaperylene and carbazole series.

The reaction is usually efiected by heating and preferably in the presence of a diluent. In manycases it may be promoted by the addition of catalytic substances, as for example copper and its compounds and/or by using agents binding acids.

The new vat dyestufls thus obtainable hav various shades of color depending on the initial.

Example 1 A mixture of 18 parts of C.4'-chlorphenylanthraquinone-NN).2-oxazole (obtained from 1- amino-2-hydroxyanthraquinone by boiling with para-chlorbenzoyl chloride in nitrobenzene) 11.3 parts of l-aminoanthraquinone, 8 parts of dehydrated sodium acetate, 1 part of copper acetate and 250 parts of nitrobenzene is heated to boiling in a stirring vessel until initial material is no longer present. After cooling, the whole is filtered off by suction and the resulting dyestuff is washed with nitrobenzene, alcoholand water and dried. It is a brown crystal powder which does not melt even at 360 C. and'which dissolves in concentrated sulphuric acid giving a green-yellow colorationwhich changes to blue-green uponthe addition of formaldehyde. It dyes vegetable fibres very fast brown-red shades from a red vat and has the following composition:

A similar dyestuff is obtained by reacting CA- aminophenylanthraquinone-1 (N) .2-oxazole with l-chloranthraquinone. f

.If 0.4'-chlorphenylanthraquinone 1.2 imidazole, or the corresponding -1(S) .-2(N) thiazole be used instead of C. l-chlorphenylanthraquinone-1(N) .3-oxazole, fast vat dyestuffs are also obtained.

. Example 2 A mixture of 18 parts of C.4-chlorphenylanthraquinone-1(N) .2-oxazo1e, 17.2 parts of 1- amino-5-benzoylaminoanthraquinone, 8 parts of anhydrous sodium acetate, 1 part of copper acetate and 250 parts of nitrobenzene is heated in a stirring vessel as described in Example 1 and worked up in the manner described therein. A

red-brown dyestuff is obtained which dissolves in concentrated sulphuric acid giving a yellow coloration which changes to green upon the addition of formaldehyde. It dyes cotton red-brown shades of very good fastness properties from a red vat.

If 1-amino-4-benzoylaminoanthraquinone be used instead of 1-amino 5-benzoylaminoanthraquinone, an olive dyestuff is obtained which dyes vegetable fibres olive shades of good fastness from a red vat.

A mixture of 18.5 parts of C.3'-nitrophenylanthraquinone uN).2-oxazole, 11.2 parts of 1- aminoanthraquinone, 8 parts of sodium acetate, 1 part of copper acetate and 200 parts of nitrobenzene is heated to boiling while stirring for about 20 hours. .The whole is then allowed to cool to about C. and the resulting dyestuff is filtered off by suction, washed with nitrobenzene, methanol and water and dried. A grey-brown powder is thus obtained which dissolves in concentrated sulphuric acid giving a yellow coloration and which dyes cotton yellow-olive shades from a red vat.

If 1-amino-5-benzoylaminoanthraquinone be used instead of l-aminoanthraquinone, a brown dyestuif is obtained which dyes cotton olive shades from a red vat.

When the oxazoles obtainable by causing 1- amino-Z-hydroxyanthraquinone or 2-amino-3- hydroxyanthraquinone to react with .nitroor halogen-methylbenzoyl chlorides are used instead of 0.3-nitrophenylanthraquinone 1(N) .2 oxazole, very fast vat dyestuffs are also obtained.

Example 4 A mixture of 20 parts of C.2'.4-dichlorphenylanthraquinone-1(N) .2-oxazole (obtainable from 1-amino-2-hydroxyanthraquinone by heating with 2,4dichlorbenzoyl chloride in nitrobenzene) 17.5 parts of1-amino-5-benzoylarninoanthraquinone, 8 parts of sodium acetate,'1 part of copper acetate and 250 parts of nitrobenzene is heated to boiling for about 15 hours while stirring. The whole is filtered by suction while hot and the residue is washed with nitrobenzene, methanol and water and dried. A dark brown crystal powder is thus obtained which dissolves in concentrated sulphuric acid giving a yellow coloration and which dyes cotton brown shades from a red 22.

Example 5 Ainixture of 1 3 parts of l-amino-2-hydroxyanthraquinone, 2 parts of 4-(1-anthraquinonylamino) -benzoyl chloride (obtainable by the reaction of para-aminobenzoic acid with l-chloran- .thraquinone and treatment of the resulting 4'-(1- anthraquinonyla nino) benzoic acid with thionyl chloride), 0.4 part of para-toluenesulphonic acid and 300 parts of nitrobenzene is heated to boiling for about 2 hours. After cooling, the whole is filtered by suction and the residue washed with nitrobenzene and alcohol. The dyestuff obtained is a red-brown powder which dissolves in concentrated sulphuric acid giving a yellow-green coloration and which dyes vegetable fibres brownred shades from a red vat. It agrees with the dyestuff obtainable according to Example 1.

If 4'-(l-anthraquinonylamino) benzoyl chloride be allowed to act on 2-hydro-xy-3-aminoanthraquinone. the corresponding 2.3-anthraquinoneoxazole is obtained; by the action on orthomercaptoaminoanthraquinones, the corresponding anthraquinonethiazole derivatives are formed.

Example 6 A mixture of 18 parts of C.4-chlorphenylanthraquinone-23-oxaz0le (obtainable by heating 2-amino3-hydroxyanthraquinonewith parachlorbenzoyl chloride in nitrobenaene), 1'7 parts of 1-amino-4benzoylaminoanthraquinone, 8 parts of sodium acetate, 1 part of copper acetate and 250 parts of nitrobenzene is heated to boiling,.While stirring, until the formation of the dyestuii is completed. After cooling, the dyestufi is filtered ofl by suction and the residue washed with nitrobenzene, methanol and Water; it is a darkgreen powder which is soluble in sulphuric acid giving a green-yellow coloration. It dyes cotton fast olive-green shades from a green-brown vat.

If instead of l-amino i-benzcylaminoanthraquinone l-aminoanthraquinone or l-aminmbenzoylaminoanthraquinone is employed, there is obtained a dyestufi giving a brown-red or brown coloration, respectively.

(3.3 chlorphenylanthraquinone, 2.3 oxazole may also be employed instead of C.4'-chlorphenylanthraquinone-2.3-oxazcle in which case the shade of color of the resulting dyestuff is rather difierent from that obtained when using CAchlorphenylanthraquinone-2.3-oxazo1e.

What I claim is:

1. A vat dyestuff of the general formula H A CRN-Z wherein A stands for the radical of an anthraquinone, X for a member selected from the class consisting of O-, S-, and NH, R for a phenylene radical and Z for an anthraquinone radical the azole ring shown being attached to adjacent positions of A, the C and NH atoms shown being linked directly to carbon atoms of the said phenylene ring and the NH group shown being linked directly to a carbon atom of the said anthraquinone nucleus.

2. A vat dyestufi of the general formula wherein R stands for a phenylene radical and Z for the radical of an anthraquinone, and C and NH atoms shown being linked directly to car- -NI-I group shown being linked directly to a carbon atom of the said anthraquinone nucleus.

4. A vat dyestufi of the general formula wherein R stands for a phenylene radical and Z for the radical of an anthraquinone, the C and NH atoms shown being linked directly to carbon atoms of the said phenylene ring and the NH group shown being linked directly to a carbon atom of the said anthraquinone nucleus.

5. The vat dyestufi of the formula 6. The vat dyestufi of the formula OTTO SCI-ILICI-ITING.

bon atoms of the said phenylene ring and the 

